Phosphinyloxyvinyl phosphorothioates



United States Patent 3,028,303 PHOPHINYLOXYVINYL PHOSPHOROTHIOATES John P. Chupp, Kirkwood, Mo., assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware N0 Drawing. Filed June 1, 1960, Ser. No. 33,096 19 Claims. (Cl. 167-22) This invention relates to new and useful phosphorothioates and to methods of making same. Additionally this invention relates to insecticidal compositions containing the new phosphorothioates as an active ingredient.

The new compounds of this invention can be termed phosphinyloxyvinyl phosphorothioates and can be represented by the structure wherein R, R" and R are like or unlike alkyl radicals containing from 1 to 5 carbon atoms (e.g. methyl, ethyl, propyl, butyl, amyl, and the various isomeric forms thereof such as isobutyl, isopropyl, etc.) but preferably containing not more than two carbon atoms; wherein X is a chalkogen of atomic weight less than 40 (i.e. sulfur or oxygen) but preferably sulfur; wherein A is a hydrocarbon radical free of non-benzenoid unsaturation (e.g. alkyl radicals free of olefinic and acetylenic unsaturation such as methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl,

and the various isomeric forms thereof; aralkyl radicals such as benzyl, cycloalkyl radicals such as cyclopentyl, cyclohexyl, methylcyclohexyl; aryl radicals such as phenyl, tolyl, and halogen substituted aryl radicals such'as the various mono-, diand tri -chloro phenyl radicals, etc.);

wherein B is hydrogen, or lower alkyl or halogen (i.e.

chlorine or bromine) but preferably hydrogen.

The phosphorothioates ofthis invention can ,beprepared by reacting a trialkyl phosphite of the structure RO-P OAlk

wherein Alk like R and R" aforedescribed is an alkyl radical containing from 1 to 5 carbon atoms but preferably 1 to 2 carbon atoms with a substantially equimolar amount of a halide of the structure II I ll 2 '-s-(CCA) halogen wherein R, X, B and A have the aforedescribed significance and wherein the term halogen means a halogen having an atomic number above 9 but not higher than 35 (i.e. chlorine or bromine). When desired an inert organic solvent such as benzene, xylene, toluene, acetone, butanone, dioxane, etc., can be used. While a wide range of reaction temperatures can be employed provided the system is fluid (i.e. above the freezing point of the system up to and including the boiling point of the system) it is preferred to employ a reaction temperature in the range of 20 C. to 120 C.

These halide reactants are readily prepared in a fluid medium from equimolar proportions of an ammonium salt of the structure 3,028,303 Patented Apr. 3, 1962 ice and an a,a-dihalogen substituted ketone, of the structure Example I To a suitable reaction vessel equipped with a thermometer, agitator and reflmc condenser is charged approximately 33.9 parts by weight (0.1 mol) of S-(a-chlorophenancyl) 0,0-diethyl phosphorodithioate and thereto at room temperature and with agitation is slowly added 12.4 parts by weight (0.1 mol) of trimethyl phosphite. The reaction is slightly exothermic and the temperature is permitted to rise to 50 C. Upon comple tion of the trimethyl phosphite addition the reaction mass is heated at -90 C. for 2.5 hours. The mass is then stripped of volatiles under 5 mm. pressure by heating to a pot temperature of C. The residue, an amber oil, is 0,0-diethy1 S-[b-(a-dimethoxyphosphinyloxy)styryl] phosphorodithioate II oorn-o-o-r-roorn Ho-s-n-wonnn which is'soluble in benzene but insoluble in water. Analysis. 'I'heory: 15.5% S. Found: 15.1% S.

Example II Employing the procedure of Example I but replacing S-(a-chlorophenacyl) 0,0-diethyl phos'phorodithioate with an equimolar amount of S-(l-chloro-Z-oxypropyl) 0,0-dimethyl phosphorodithioate an amber oil which is soluble in benzene and acetone but insoluble in water.

Example Ill Employing the same procedure as in Example I but replacing trimethyl phosphite with an equimolar amount of triethyl phosphite there is obtained in a quantitative 3 yield opaiah i S-lib-(a-diethoxyphosphinyloxy) styryl] pho sphorodithioate an amber oil which is soluble in benzene but insoluble in water. I

Analysis-Theory: 14.3%. Found: 14.6% S.

Example IV Employing the same procedure as in Example I but replacing 0,0 diethyl S-(a-chlorophenacyl) phosphorodithioate with an equimolar amount of 0,0-diethyl S-(a, 4-dich1orophenacyl) phosphorodithioate there is obtained Q,O-diethyl S-[4-chloro b-(a-dimethoxyphosphinyloxy) styryl] phosphorodithioate if GlCuHr C-O-P(OCH' HC-SP(OCgH an amber oil which is soluble in benzene but insoluble in water. I v

Analysis.Theory: 13.5% S. Found: 13.2% S.

Example V Employing the same procedure as in Example I but replacing 0,0-diethyl S-(a-chlorophenacyl) phosphorodithioate with anequirnolar amount of 0,0 -diethy1 S-( lchloro-z-oxy-butyl) phosphorothioate there is obtained as an, 0,0-'diethyl S-[b (a ethyl,a-dimethoxyphosphinyloxywin n phosphorothioate which is soluble in acetone but insoluble in water.

Example VI Employing the same procedure as in Example I but replacing O,O-diethyl S-(a-chlorophenacyl) phosphorodithioate with an equimolar amount of 0,0-diisopropyl S-(2-bron1o-3-oxy-butyl) phosphorothioate there is obtained 0,0-diisopropyl S [b-rnethyl-b-(amethyl-a-dimethoxyphosphinyloxwvinyl] phosphorothioate an oil which is'soluble in acetone but insoluble in water.

Example VII Employing the same procedure as in Example I but replacing 0,0-diethyl S-(a-chlorophenacyl) phosphorodithioate with an equimolar amount of 0,0-dimethyl S- (a,a-dichlorophenacyl) phosphorothioate there is obtained 0,0-d-imethyl S [b-chloro-b(a-dimethoxyphosphinyloxy) styryl] 'phosphorothioate an oil which is soluble in benzene but insoluble in water.

4 Example VIII Employing the same procedure as in Example I but replacing 0,0-diethyl S-(a-chlorophenacyl) phosphorodithioate with an equirnolar amount of 0,0-diethyl S-(a, 2,4,5-tetrachlorophenacyl) phosphorodithioate there is obtained 0,0-diethyl S-[2,4,5-trichloro-b-(a-dirnethoxyphosphinyloxy)styryl] phosphorodithioate an oil which is soluble in benzene but insoluble in water.

Example IX Employing the procedure of Example I but replacing trimethyl phosphite with an equimolar amount of tributyl phosphite there is obtained QO-diethyl S-[b-(a-dibutoxyphosphinyloxy)styryl] phosphorodithioate, an oil which is soluble in benzene but insoluble in Water.

Example X Employing the procedure of Example I but replacing trimethyl phosphite with an equimolar amount of ethyl diisoamyl phosphite there is obtained QO-diethyl S-[b-(adiisoamyloxyphosphinyloxy) styryl] phosphorodithioate, an oil which is soluble in benzene but insoluble in water.

Other phosphite reactants than those specifically set forth above can be employed in preparing the phosphorothioates of this invention, e.g. tripropyl phosphite, triisopropyl phosphite,triisobutyl phosphite, methyl diisobuty-l phosphite, tri-secbutyl phosphite, triamyl phosphite, etc. Also other halide reactants which satisfy the structure I! ll (ROM-P-S (-C-O-A) halogen wherein R, X, B, A and halogen have the aforedescribed significance can be employed than those specifically set forth above. It is preferred that X be sulfur and that B be hydrogen. In general A will contain not more than 7 carbon atoms and it is particularly preferred that A be a phenyl radical of the empirical formula C I-I Cl wherein n isan integer from 0 to 3, e.g. phenyl, 3-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,4,5-trichlorophenyl, 2;4,6-trichlorophenyl etc. As further illustrative of such halide reactants are:

It will be understood that the terms insect and insecticide are used herein in their broad common usage to include spiders, mites, ticks, and like pests which are not in the strict biological sense classed as insects. Thus the usage herein conforms to the definitions provided by Congress in Public Law 104, the Federal Insecticide, Fungicide, and Rodenticide Act of 1947, Section 2, subsection h, wherein the term insect is used to refer not only to those small invertebrate animals belonging most- 1y to the class Insecta, comprising six-legged, usually winged forms, as beetles, bugs, bees, flies, and so forth, but also to other allied classes of arthropods whose members are Wingless and usually have more than six legs, as spiders, mites, ticks, centipedes, and wood lice.

The phosphorothioates of this invention are effective against a wide variety of insect pests. As illustrative of the activity but not limitative thereof is the following:

One gram of S-[b-(a-diethoxyphosphinyloxy)styryl] 0,0-diethyl phosphorodithioate is dissolved in sufiicient acetone to make a concentrate solution thereof. Approximately 0.1 cc. of sorbitan monolaurate polyoxyethylene derivative (a commercial water-soluble non-ionic emulsifying agent containing 20 moles of ethylene oxide per mole of sorbitan monolaurate) is then mixed with the concentrate. To this mixture and with agitation is added sufiicient water to provide an aqueous emulsion having a concentration of 0.006% by weight of S-[b-(adiethoxyphosphinyloxy)styryl] 0,0-diethyl phosphorodithioate. Thereupon lima bean plant leaves previously infested with the two-spotted spider mite, Tetranychus telarz 'us (L.), are dipped in the aqueous emulsion, withdrawn, and set aside for observation. At the end of 48 hours a 100% kill of the mobile stage of the mite is noted. Seven days after setting the test specimen aside, residual activity is confirmed, a 90% kill of both the resting stage and the ova stage being noted. Similar results against the mobile, resting and ova stages of the same mite are obtained employing S-[4-chloro-b-(-a-dimeth'oxyphosphinyloxy)styryl] 0,0-diethyl phosphorodithioate at the same concentration.

Employing the phosphorodithioates of Examples I, III, and IV, respectively, at concentrations of 0.00006% against yellow fever mosquito larvae, Aedes aegypti, 100% kills are observed.

Although the phosphorothioates of this invention are useful per se in controlling a wide variety of insect pests, it is preferable that they be supplied to the pests or to the environment of the pest or pests in a dispersed form in a suitable extending agent.

In the instant specification and appended claims it is to be understood that the term dispersed is used in its widest possible sense. When it is said that the phosphorothioates of this invention are dispersed, it means that the particles of the phosphorothioates of this invention may be molecular in size and held in true solution in a suitable organic solvent. It means further that the particles may be colloidal in size and distributed throughout a liquid phase in the form of suspensions or emulsions or in the form of particles held in suspension by wetting agents. It also includes particles which are distributed in a semi-solid viscous carrier such as petrolatum or soap or other ointment base in which they may be actually dissolved in the semi-solid or held in suspension in the semi-solid with the said of suitable wetting or emulsifying agents. The term dispersed also means that the particles may be mixed with and distributed throughout a solid carrier providing a mixture in particulate form, e.g. pellets, granules, powders, or dusts. The term dispersed also includes mixtures which are suitable for use as aerosols including solutions, suspensions, or emulsions of the phosphorothioates of this invention in a carrier such as dichloro-difiuoromethane and like fluorochloroalkanes which boil below room temperature at atmospheric pressure.

In the instant specification and appended claims it is to be understood that the expression extending agen includes any and all of those substances in which the phosphorothioates of this invention are dispersed. It includes, therefore, the solvents of a true solution, the liquid phase of suspensions, emulsions or aerosols, the semi-solid carrier of ointments and the solid phase of particulate solids, e.g. pellets, granules, dusts and powders.

The exact concentration of the phosphorothioates of this invention employed in combatting or controlling insect pests can vary considerably provided the required dosage (i.e. toxic or lethal amount) thereof is supplied to the pests or to the environment of the pests. When the extending agent is a liquid or mixture of liquids (e.g. as in solutions, suspensions, emulsions, or aerosols) the concentration of the phosphorothioate employed to supply the desired dosage generally will be in the range of 0.001 to 50 percent by weight. When the extending agent is a semi-solid or solid, the concentration of the phosphorothioate employed to supply the desired dosage generally will be in the range of 0.1 to 25 percent by weight. From a practical point of view, the manufacturer must supply the agriculturist with a low-cost concentrate or spray base or particulate solid base in such form that, by merely mixing with water or solid extender (e.g., powdered clay or talc) or other low-cost material available to the agriculturist at the point of use, he will have an easily prepared insecticidal spray or particulate solid. In such a concentrate composition, the phosphorothioate generally will be present in a concentration of 5 to 95 percent by weight, the residue being any one or more of the well-known insecticidal adjuvants, such as the various surface active agents (e.g. detergents, a soap or other emulsifying or wetting agent), surface-active clays, solvents, diluents, carrier media, adhesives, spreading agents, humectants, and the like.

There are a large number of organic liquids which can be used for the preparation of solutions, suspensions or emulsions of the phosphorothioates of this invention. For example, isopropyl ether, acetone, methyl ethyl ketone, dioxane, cyclohexanone, carbon tetrachloride, ethylene dichloride, tetrachloroethane, hexane, heptar'ie and like higher liquid alkanes, hydrogenated naphthalenes, solvent naphtha, benzene, toluene, xylene, petroleum fractions (e.g. those boiling almost entirely under 400 F., and having a flash point above about F., particularly kerosene), mineral oils having an unsulfonatable residue above about 80 percent and preferably above about percent. In those instances wherein there may be concern about the phytoxicity of the organic liquid extending agent a portion of same can be replaced by such low molecular weight aliphatic hydrocarbons as dipentene, diisobutylene, propylene trimer, and the like or suitable polar organic liquids such as the aliphatic e-thers and the aliphatic ketones containing not more than about 10 carbon atoms as exemplified by acetone, methyl ethyl ketone, diisobutyl ketone, dioxane, isopropyl ether, and the like. In certain instances, it is advantageous to employ a mixture of organic liquids as the extending agent.

When the phosphorothioates of this invention are to be supplied to the insect pests or to the environment of the pests as aerosols, it is convenient to dissolve them in a suitable solvent and disperse the resulting solution in dichlorodifluorornethane or like chlorofiuoroalkane which boils below room temperature at atmospheric pressure.

The phosphorothioates of this invention are preferably supplied to the insect pests or to the environment of the insect pests in the form of emulsions or suspensions. Emulsions or suspensions are prepared by dispersing the phosphorothioate of this invention either per se or in the form of an organic solution thereof in water with the aid of a water-soluble surfactant. The term surfactant as employed here and in the appended claims is used as in volume II of Schwartz, Perry and Berchs Surface Active Agents and Detergents (1958, Interscience Publishers, Inc., New York) in place of the expression emulsifying agent, to connote generically the various emulsifying agents, dispersing agents, wetting agents and spreading agents that are adapted to be admixed with the active compounds of this invention in order to secure better wetting and spreading of the active ingredients in the water vehicle or carrier in which they are insoluble through lowering the surface tension of the water (see also Frea Chemistry of Insecticides, Fungicides and Herbicides, Second edition, page 280). These surfactants include the well-known capillary active substances which may be anion-active (or anionic), cation active (or cationic), or non-ionizing (or non-ionic) which are described in detail in volumes I and II of Schwartz, Perry and Berohs Surface Active Agents and Detergents 195 8, Interscience Publishers, Inc., New York) and also in the November 1947 issue of Chemical Industries (pages 811-824) in an article entitled Synthetic Detergents by John W. McCutcheon and also in the July, August, September and October 1952 issues of Soap and Sanitary Chemicals under the title Synthetic Detergents. The disclosures of these articles with respect to surfactants, i.e. the anion-active, cation-active and non-ionizing capillary active substances, are incorporated in this specification by reference in order to avoid unnecessary enlargement of this specification. The preferred surfactants are the water-soluble anionic surface-active agents and the water-soluble non-ionic surface-active agents set forth in US. 2,846,398 (issued August 5, 1958). In general it is preferred that a mixture of water-soluble anionic and water-soluble non-ionic surfactants be employed.

The phosphorothioates of this invention can be dispersed by suitable methods (e.g., tumbling or grinding) in solid extending agents either of organic or inorganic nature and supplied to the insect pests environment in particulate foarm. Such solid materials include for example, tricalcinm phosphate, calcium carbonate, kaolin, bole, kieselguhr, talc, bentonite, fullers earth, pyrophillite diatomaceous earth, calcined magnesia, volcanic ash, sulfur and the like inorganic solid materials, and include for example, such materials of organic nature as powdered cork, powdered wood, and powdered walnut shells. The preferred solid carriers are the adsorbent clays, e.g. bentonite. These mixtures can be used for insecticidal purposes in the dry form, or by addition of water-soluble surfactants or wetting agents the dry particulate solids can be rendered wettable by water so as to obtain stable aqueous dispersion or suspensions suitable for use as sprays.

For special purposes the phosphorothioates of this invention can be dispersed in a semi-solid extending agent such as petrolatum or soap (e.g. sodium stearate or oleate or palmitate or mixtures thereof) with or without the aid of solubility promoters and/or surfactants or dispersing agents.

In all of the forms described above the dispersions can be provided ready for use in combatting insect pests or they can be provided in a concentrated form suitable for mixing with or dispersing in other extending agents. As illustrative of a particularly useful concentrate is an intimate mixture of phosphorothioate of this invention with a water-soluble surfactant which lowers the surface tension of water in the weight proportions of 0.1 to 15 parts of surfactant with sufiicient of the phosphorothioate of this invention to make 100 parts by weight. Such a concentrate is particularly adapted to be made into a spray for combatting various forms of insect pests (particularly mites) by the addition of water thereto. As illustrative of such a concentrate is an intimate mixture of 95 parts by weight of S-[b-(a-diethoxyphosphinyloxy)styryl] 0,0-diethyl phosphorodithioate and parts by weight of a water-soluble non-ionic surfactant such as the polyoxyethylene derivative of sorbitan monolaurate.

Another useful concentrate adapted to be made into a spray for combat-ting insect pests (particularly mites) is a solution (preferably as concentrated as possible) of a phosphorothioate of this invention in an organic solvent therefor.

The said liquid concentrate preferably contains dissolved therein a minor amount (erg, 0.5 to 10 percentby weight of the weight of the new insecticidal agent) of a surfactant (or emulsifying agent), which surfactant is also Water-soluble. As illustrative of such a concentrate is a solution of S-[4-chloro-b-(a-dimethoxyphosphinyloxy)styryl] 0,0-diethyl phosphorodithioate in benzene which solution contains dissolved thereina watersoluble polyoxyethylene glycol non-ionic surfactant and a water-soluble alkylaryl sulfonate anionicsu'rfactant.

Of the surfactants aforementioned in preparing the various emulsifiable, Wettable ordispersible compositions or concentrates of this invention, the anionic and nonionic surfactants are preferred. Of this anionic surfactants, the particularly preferred are the well-known watersoluble alkali metal alkylaryl sulfonates as exemplified by sodium decylbenzene sulfonate and sodium dodecylbenzene sulfonate. Of the non-ionic surfactants, the particularly preferred are the water-soluble polyoxyethylene derivatives of alkylphenols (particularly isooctylphenol) and the water-soluble polyoxyethylene derivatives of the mono-higher fatty acid esters of sorbitan containing 15 to 30 moles of ethylene oxide per mole of sorbitan monoester or alkylphenol.

In all of the various dispersions described hereinbefore for insecticidalpurposes, the active ingredient can be one or more of the compounds of this invention. The compounds of this invention can also be advantageously employed in combination with other pesticides, including, for example, nematocides, bactericides, and herbicides. In this manner it is possible to obtain mixtures which are effective against a wide variety of-pests and other forms of noxious life.

In controlling or combatting insect pests the phosphorothioates of this invention either per se or compositions comprising same are supplied to the insect pests or to their environment ina lethal or toxic amount. 'This can be done by dispersing the new insecticidal agent or insecticidal composition comprising same'in, on or over an infested environment or in, on or over an'environment the insect pests frequent, e.g., agricultural soil or other growth media or other media infested with the insect pests or attractable to the pests for habitational or sustenance or propagational purposes, in any conventional fashion which permits contact between the insect pests and the phosphorothioate of this invention. Such dispersing can be brought about by applying sprays or particulate solid compositions to a surface infested with the insect pests or attractable to the pests, as for example, the surface of an agricultural soil or other media such as'the above ground surface of plants by any of the conventional methods, e.g. power dusters, boom and hand sprayers and spray clusters. Also for sub-surface application such dispersing can be carried out by simply mixing the new insecticidal agent per se or insecticidal spray or particulate solid compositions comprising same with the infested environment or with the environment the insect vpests frequent, or by employing a liquid carrier for the new insecticidal agent to accomplish sub-surface penetration and impregnation therein.

While this invention has been described with respect to certain embodiments, it is to be understood that it is not solimited and that variations and modifications thereof obvious to those skilled in the art can be made without departing from the spirit and scope thereof.

What is claimed is:

'1. Phosphorothioates of the structure B-C-s- OR wherein lL R'v and .R.are alkylradicals containing from 1 to 5 carbon atoms; whereinX is a chalkogen of atomic weightless than 40; wherein A is selected from the group consisting of hydrocarbon radicals containing not more than 7 carbon atoms which are free of non-benzenoid unsaturation and chloro phenyl radicals; and wherein B is selected from the group consisting of hydrogen, lower alkyl radicals, and halogen having an atomic number above 9 but not higher than 35.

2. Phosphorothioates of the structure wherein R, R and R" are alkyl radicals containing not more than 2 carbon atoms and wherein A is a phenyl radical having the empirical formula C I-I,-, ,,Cl wherein n is an integer from to 3.

3. A compound of the structure 4. A compound of the structure 5. A compound of the structure 6. A compound of the structure 0 C GA m C2115)? 7. The method of making the phosphorothioates of the structure 0 on A-o-o i BOS-P-(OR)1 wherein R, R and R" are alkyl radicals containing 1 to 5 carbon atoms; wherein X is a chalkogen of atomic weight less than 40; wherein A is selected from the group consisting of hydrocarbon radicals containing not more than 7 carbon atoms which are free of non-benzenoid unsaturation and chlorophenyl radicals containing not more than 3 chlorine substituents; and wherein B is selected from the group consisting of hydrogen, lower alkyl radicals, and halogen having an atomic number above 9 but not higher than 35, which comprises reacting a trialkyl phosphite of the structure wherein R and R" have the same significance as in above and wherein Alk means an alkyl radical containing 10 from 1 to 5 carbon atoms with a substantially equimolar amount of a halide of the structure i u (RO)91LS(-C-CA) halogen wherein R, X, B and A have the same significance as in above and wherein halogen means a halogen having an atomic number above 9 but not higher than 35.

8. The method of claim 7 wherein Alk means an alkyl radical containing not more than two carbon atoms, wherein X is sulfur, and wherein B is hydrogen.

9. The method of making the phosphorothioates of the structure fi o R A-CO-P 0 RI I wherein R, R and R" are alkyl radicals containing not more than 2 carbon atoms and wherein A is a phenyl radical having the empirical formula C H ,,Cl wherein n is an integer from 0 to 3, which comprises reacting a trialkyl phosphite of the structure RO-P O-Alk wherein R, R and Alk mean alkyl radicals containing not more than two carbon atoms with a substantially equimolar amount of a halide of the structure wherein R is an alkyl radical containing not more than two carbon atoms, wherein A is a phenyl radical of the empirical formula C H Cl,, wherein n is an integer from 0 to 3, and wherein halogen means a halogen having an atomic number above 9 but not higher than 35.

10. The method of protection of plants against insect attack which comprises applying to the plant an insecticidal amount of at least one compound of claim 1.

11. An insecticidal composition comprising a compound of claim 1 dispersed in an extending agent.

12. An insecticidal composition comprising a compound of claim 1 dispersed in an extending agent, the composition containing 0.1 to 25 percent by weight of said compound of claim 1, the extending agent being selected from the group consisting of solid and semi-solid extending agents.

13. An insecticidal composition comprising a compound of claim 1 dispersed in a liquid extending agent, the composition containing 0.001 to 50 percent by weight of said compound of claim 1.

14. An insecticidal composition comprising a compound of claim 2 dispersed in an adsorbent clay, the composition containing 0.1 to 25 percent by weight of said compound of claim 2.

15. An insecticidal concentrate comprising a compound of claim 2 and an insecticidal adjuvant, said concentrate containing from 5 to percent by weight of the compound of claim 2.

16. An insecticidal concentrate comprising a compound of claim 2 dispersed in an organic solvent therefor and having dissolved therein a minor amount of a surfactant, said concentrate forming an emulsion with water upon agitation therewith.

17. An insecticidal concentrate adapted to be made into a sprayable composition by the addition of water comprising a compound of claim 2 in admixture with a water-soluble surfactant in the weight proportion of 0.1 to 15 parts of surfactant and suflicient of said compound of claim 2 to make parts by weight.

18. The method of controlling insects which comprises contacting the insects with a lethal amount of a compound of claim 1.

19. The method of controlling insects which comprises contacting the insects with a lethal amount of a com pound of claim 2.

References Cited in the file of this patent UNITED STATES PATENT$ Scherer et a1 May 5, 1959 Stiles July 21, 1959 Willard et a1. -n Mar. 15, 1960.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,028,303 April 3, 1962 John P. Chupp It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, line 11, for "14.3%." read 14.3% S. column 4, lines 38 to 41, the formula should appear as shown below instead of as in the patent:

halogen column 5, line 36, for "(-=adi-" read (adi line 62, for "said" read aid column 7, line 6, for "Frea" read Frear line 33, for "foarm" read form column 9, line 74, strike out "in"; column 10, line 7, strike out "in".

Signed and sealed this 7th day of August 1962.

(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting- Qfficer Commissioner of Patents 

1. PHOSPHOROTHIOATES OF THE STRUCTURE 